The effect of fulvic acid on the sorption of actinides and fission products on granite and selected minerals

Organic material is present at low concentrations, typically 1–2 mg/l in terms of dissolved organic carbon (DOC), in groundwaters deep in granitic rock. Hydrophobic and hydrophilic acids may complex inorganic contaminants and change their sorption behaviour on geological materials. This report describes a series of experiments performed under aerobic conditions to investigate the effects of fulvic acid over a concentration range of 0–5 mg/I DOC on the sorption of⁸⁵Sr,¹³⁷Cs,²³³U,²³⁸Pu and²⁴¹'Am by crushed granite, biotite, goethite, montmorillonite and quartz. In addition, similar solutions were used to study the effects of dissolved fulvic acid on the sorption of⁹⁹Tc and¹²⁵I on each of the above solids except quartz. The fulvic acid was extracted from groundwater collected at a depth of 240 m in the granitic rock of the Underground Research Laboratory near Lac du Bonnet, Manitoba.In all experiments, the sorption of the fulvic acid by the geological materials was in the order goethite montmorillonite > biotite > granite > quartz. No sorption of Tc was observed from any of the solutions on any of the solids. Low sorption of I on montmorillonite occurred in the presence of the dissolved organic material. No sorption of I was observed with the other solids used. Only montmorillonite sorbed any appreciable amount of Sr in this study with the fulvic acid having no effect on this sorption. All the solids except quartz sorbed substantial amounts of Cs, but sorption was not affected by the organic material in solution. Each of the solids sorbed U with no difference in sorption observed due to the dissolved organic. In general, Pu sorption decreased as the concentration of dissolved fulvic acid increased. However, sorption of Pu on quartz remained at approximately the same levels regardless of the concentration of organic in solution. Generally high sorption of Am was found. Lowest sorption of Am on all solids occurred from the solution with the highest concentration of fulvic acid. Sorption of Am on granite decreased as the concentration of the organic in solution increased.This study indicated that, under aerobic conditions, the effect of dissolved organic material on sorption of radioisotopes depends on the radioisotope in question and the concentration of the organic in solution.     

The pore water chemistry of 239,240Pu and 137Cs in sediments of Buzzards Bay,Massachusetts

The collection of large volumes of pore water (1–2 liters per 2 cm horizon of sediment) and low level radiochemical measurements of ^239,240Pu and ¹³⁷Cs have been combined to produce the first study of these fallout artificial radionuclides in marine pore waters. Profiles from box cores taken in June and September 1982 from Buzzards Bay, Mass., are reported along with profiles of many diagenetic constituents (i.e. SO₄^2?, alkalinity, Fe, Mn, DOC, and nutrients).The ^239,240Pu pore water profile is characterized by a subsurface maximum of about 0.28 dpm/100 kg lying between 3–11 cm. Overlying seawater, in contrast, has an activity of $\text{0.01 ± 0.02}$ dpm/100 kg. Below about 11 cm, the pore water ^239,240Pu distribution follows that of the solid phase which decreases rapidly with depth. The pore water profiles of ¹³⁷Cs are characterized by a broad and deeply penetrating maximum where activities of about 35–40 dpm/100 kg extend from 3 to 20 cm. Overlying seawater, in contrast, has an activity of 17–24 dpm/100 kg. The ¹³⁷Cs and ^239,240Pu pore water data show that there is preferential downward transport of ¹³⁷Cs and that ^239,240Pu does not have an active diagenetic chemistry and is not significantly mobile in these coastal sediments.     

Laboratory and field studies of the relative mobility of 239,240Pu and 241Am from lake sediments under oxic and anoxic conditions

Laboratory extraction experiments and field observations were employed to determine the relative mobility of ^239,240pu and ²⁴¹Am from lake sediments under aerobic and anaerobic conditions. Laboratory investigations show that under aerobic conditions ²⁴¹Am is more readily extracted from Lake Michigan sediments than is ^239,240Pu. Under anaerobic conditions, the extractability of plutonium and americium does not increase significantly relative to aerobic conditions. Field studies indicate that neither element is recycled from the sediment to the overlying water column during anaerobic conditions attendant with thermal stratification. The adsorption of these elements onto sediments does not appear to be correlated with extractable iron, manganese, and organic compounds such as humic and fulvic acids.     

Laboratory studies of the diagenesis and mobility of 239,240pu and 137Cs in nearshore sediments

Controlled laboratory experiments have been used to study the diagenetic chemistry of ^239,240Pu ¹³⁷Cs, and ⁵⁵Fe. Experiments using Buzzards Bay sediments in small tanks show that sulfate reduction is accompanied by the production of large pore water concentration gradients of alkalinity, phosphate, ammonia and dissolved organic carbon and the formation of subsurface maxima in Fe and Mn. These pore water profiles demonstrate that bacterially-mediated processes of organic matter degradation and redox reactions can be simulated in the laboratory.A vertical profile of ⁵⁵Fe in pore waters is reported for the first time: it follows the profile of stable Fe and as such has a large (200 dpm/100 kg) subsurface maximum between 2–4 cm depth. Comparison of ⁵⁵Fe/Fe ratios in sediments and pore waters shows that there is preferential solubilization of ⁵⁵Fe over stable Fe.The pore water activities of ^239,240Pu show no gradients within the large uncertainties of the counting statistics, but are two to four times higher than Buzzards Bay seawater (0.05 dpm/100 kg).The activity of ¹³⁷Cs in the pore water profile is constant (40 dpm/100 kg) within the large counting uncertainties and is twice that of Buzzards Bay seawater. Cs-137 does not appear to be involved in diagenetic chemistry but may increase in pore waters as a result of ion exchange reactions.Flux estimates based on the pore water data show that remobilization and transport of ^239,240 Pu in coastal sediments are not significant processes while the transport of ^l37Cs may be.     

Transport and accumulation of actinide elements in the near-shore environment: field and modelling studies

Nuclear facilities in coastal locations often discharge low‐level liquid wastes into the sea and the radioisotopes in these discharges are of interest both in assessing possible environmental impacts and as tracers for coastal processes. The distributions of a range of artificial radionuclides, derived from the authorized discharges from British Nuclear Fuels (BNFL) Sellafield, have been determined in the sediments of an intertidal salt marsh in the Esk Estuary, Cumbria, UK. Where published discharge histories exist (for ¹³⁷Cs, ²³⁸Pu, ^239,240Pu and ²⁴¹Am), the sediment core‐profile distributions of these radionuclides have been compared with the releases from Sellafield, and consistent values of the accumulation rate (0·226 ± 0·007 g cm^?2 yr^?1) are obtained. A quantitative model has been developed, describing association of radionuclides with suspended particulate material, which is then accumulated and mixed in an offshore mud patch before resuspension and deposition in the salt marsh. The model has been used to describe radionuclide distributions observed in both the mud patch and the salt marsh, and to identify isotopes for which post‐depositional remobilization or solution transport from the discharge point are important. The behaviour of the commonly studied isotopes (¹³⁷Cs, ²³⁸Pu, ^239,240Pu and ²⁴¹Am) is similar to that observed at this and other nearby locations. The activation product isotope ²³⁶U is enhanced in these sediments over the natural baseline by four to eight orders of magnitude, and the results suggest that Sellafield‐derived uranium is comparably mobile to ¹³⁷Cs in these sediments although the processes governing the behaviour of these two elements may be different. In situ production of ²⁴¹Am by decay of its ²⁴¹Pu parent has generated only 17% of the current sediment inventory of this isotope, insufficient to account for the increase over the last 20–25 years, and suggesting that the input material for these sediments is preferentially enriched in Am relative to Pu during transport from the offshore mud patch. The discharge history of ²⁴⁴Cm, which is unknown, has also been reconstructed from the sediment profile and the model.     

Sorption reversibility kinetics in the ternary system radionuclide–bentonite colloids/nanoparticles–granite fracture filling material

The kinetics of radionuclide desorption from bentonite colloids and subsequent sorption onto fracture filling material can influence colloid-facilitated radionuclide migration in ground water. To shed light on the significance of these issues batch-type experiments using a cocktail of strong and weak sorbing radionuclides as well as FEBEX bentonite colloids in the presence of fracture filling material from Grimsel (Switzerland) under Grimsel ground water conditions have been conducted. Results show that tri- and tetravalent radionuclides, ²³²Th(IV), ²⁴²Pu(IV) and ²⁴³Am(III) are clearly colloid associated in contrast to ²³³U(VI), ²³⁷Np(V) and ⁹⁹Tc(VII). Concentrations of colloid-borne ²³²Th(IV), ²⁴²Pu(IV) and ²⁴³Am(III) decrease after ∼100 h showing desorption from bentonite colloids while ²³³U(VI) and ⁹⁹Tc(VII) concentrations remain constant over the entire experimental time of 7500 h thus showing no interaction either to colloids or to the fracture filling material. ²³²Th(IV) and ²⁴²Pu(IV) data yield a slower dissociation from colloids compared to ²⁴³Am(III) indicating stronger RN–colloid interaction. In the case of ²³⁷Np(V), a decrease in concentration after ∼300 h is observed which can be explained either by slow reduction to Np(IV) and subsequent sorption to mineral surfaces in accordance with the evolution of pe/pH and/or by a slow sorption onto the fracture filling material. No influence of the different fracture filling material size fractions (0.25–0.5 mm, 0.5–1 mm and 1–2 mm) can be observed implying reaction independence of the mineral surface area and mineralogical composition. The driving force of the observed metal ion desorption from colloids is binding to fracture filling material surfaces being in excess of the available colloid surface area (76:1, 55:1 and 44:1 for the 0.25–0.5 mm, 0.5–1 mm and 1–2 mm size fraction of the FFM, respectively).     

Benthic fluxes and porewater concentration profiles of dissolved organic carbon in sediments from the North Carolina continental slope

Numerous studies of marine environments show that dissolved organic carbon (DOC) concentrations in sediments are typically tenfold higher than in the overlying water. Large concentration gradients near the sediment–water interface suggest that there may be a significant flux of organic carbon from sediments to the water column. Furthermore, accumulation of DOC in the porewater may influence the burial and preservation of organic matter by promoting geopolymerization and/or adsorption reactions. We measured DOC concentration profiles (for porewater collected by centrifugation and “sipping”) and benthic fluxes (with in situ and shipboard chambers) at two sites on the North Carolina continental slope to better understand the controls on porewater DOC concentrations and quantify sediment–water exchange rates. We also measured a suite of sediment properties (e.g., sediment accumulation and bioturbation rates, organic carbon content, and mineral surface area) that allow us to examine the relationship between porewater DOC concentrations and organic carbon preservation. Sediment depth-distributions of DOC from a downslope transect (300–1000 m water depth) follow a trend consistent with other porewater constituents (ΣCO₂ and SO₄²⁻) and a tracer of modern, fine-grained sediment (fallout Pu), suggesting that DOC levels are regulated by organic matter remineralization. However, remineralization rates appear to be relatively uniform across the sediment transect. A simple diagenetic model illustrates that variations in DOC profiles at this site may be due to differences in the depth of the active remineralization zone, which in turn is largely controlled by the intensity of bioturbation. Comparison of porewater DOC concentrations, organic carbon burial efficiency, and organic matter sorption suggest that DOC levels are not a major factor in promoting organic matter preservation or loading on grain surfaces. The DOC benthic fluxes are difficult to detect, but suggest that only 2% of the dissolved organic carbon escapes remineralization in the sediments by transport across the sediment-water interface.     

Vertical profile of artificial radionuclide concentrations in the Central Arctic Ocean

The artificial radionuclides ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu and ²⁴¹Am have been measured in eight water samples collected in 1979, at intervals from surface to bottom, through the ice at the LOREX satellite camp SS near the North Pole. Differences in the concentrations and ratios of these nuclides, compared with values measured, over time, in the various water masses that flow into the Arctic Ocean, can be used as semi-independent checks on rates of flow to the LOREX stations and on residence times in the Arctic Ocean. An unexpected finding was that water labelled with low-level liquid waste from the Windscale plant on the Irish Sea is a major component of the 1500 m LOREX sample, and has reached there in no more than eight to ten years. Even from this one station in the Polar Ocean, estimation of the inventories of the various radionuclides is good enough to emphasize the importance of horizontal advection of the various supply terms to the Arctic.     

Manzala lagoon, Nile delta, Egypt: modern sediment accumulation based on radioactive tracers

 This study was undertaken to determine whether recent anthropogenic changes in the Nile basin have affected the modern rate of sediment accumulation in the Nile delta. Excess ²¹⁰Pb, ¹³⁷Cs, and ^239,240Pu were used to develop a sediment chronology for a core from central Manzala lagoon, the delta sector which has had the highest average rate of sediment accumulation during the Holocene (to about 0.7 cm year^–1). Excess ²¹⁰Pb was detected in the top 32 cm of the core, yielding an accumulation rate of 1.2 cm year^–1, higher than the mean rate for the Holocene. A high ¹³⁷Cs/^239,240Pu ratio requires a reactor source (possibly Chernobyl) for these nuclides. Low concentrations of excess ²¹⁰Pb and weapons-fallout nuclides precluded recognition of changes in sediment accumulation rate in Manzala lagoon during this century and may limit the use of tracer radionuclides for modern sediment chronology in the Nile delta. Received: 18 March 1997 · Accepted: 22 July 1997     

Particle mixing rates in sediments of the eastern equatorial Pacific: Evidence from 210Pb, 239,240Pu and 137Cs distributions at MANOP sites

Particle mixing rates (D_B) calculated from excess ²¹⁰Pb gradients in sediments of the east equatorial Pacific range from 0.04 to 0.5 cm²/y, with variation of a factor of 3–4 at a single site. Diffusion of the ²³⁶Ra daughter ²²²Rn may affect ²¹⁰Pb distributions under conditions of slow mixing and low ²¹⁰Pb flux to the seafloor, as shown by a siliceous ooze-clay core which contained the fallout radionuclides ^239,240Pu and ¹³⁷Cs but no excess ²¹⁰Pb (relative to ²²⁶Ra). There is no clear relationship between ²¹⁰Pbderived mixing rates and sediment type, accumulation rate or organic carbon flux to the sediments. Comparison of ²¹⁰Pb mixing rates with those calculated from ^239,240Pu and ¹³⁷Cs distributions reveals better agreement for a pulse input of the fallout radionuclides (D_B = 0.03?0.4 cm²/y) than for continuous input at a constant rate (D_B = 0.1?1.6 cm²/y), although the Pu and ¹³⁷Cs data are better fit by the latter model. The agreement may be fortuitous because ^239,240Pu and ¹³⁷Cs appear significantly deeper than ²¹⁰Pb in at least one core. Tracer separation could be caused by particle size-selective mixing by the benthic fauna or by chemical mobilization. If the fallout radionuclides are scavenged from surface waters by large, organic-rich particles such as fecal pellets, their release and migration may result from decomposition of the carrier in surface sediments. Either a relatively unreactive form of Pu (e.g. oxidized Pu) has been released by this process or a one-dimensional model is inadequate to explain its observed penetration into the sediments. Activity ratios of ${}^{\mathrm{239,240}}\text{Pu}{}^{137}\text{Cs}$ in the sediments decrease with increasing north latitude, and the trend reflects higher fluxes of ^239,240Pu near the weapons test site at Christmas Island (2°N). The ${}^{\mathrm{239,240}}\text{Pu}{}^{137}\text{Cs}$ ratios and fluxes to the sediment (assuming constant input) at the siliceous ooze-red clay site are consistent with published sediment trap data from a nearby site. Thus if fallout radionuclide fluxes to the sea floor were higher in the past, both ^239,240Pu and ¹³⁷Cs have been released from sinking particles.     

Plutonium and radiocesium in the water column of the Hudson River estuary

Isotopes of plutonium (Pu), cesium (Cs), and cobalt (Co) introduced into the Hudson River Estuary from fallout deposition, the erosion of fallout-contaminated surface soils, and nuclear reactor effluent (isotopes of Cs and Co only) have been measured in water column samples collected from 1975 to 1980 Isotopic measurements conducted independently by two research groups utilizing different sampling and analytical techniques have been summarized. The major conclusions drawn from the work are that for water samples collected by the two laboratories over similar time periods, the mean concentrations of nonfilterable^239,240Pu (<0.45 μm) were identical at 0.13 fCi/l, mean concentrations of both¹³⁷Cs and^239,240Pu in suspended particulates were more divergent at 2,270±920 pCi/kg (±1 SD) and 1,430±430 pCi/kg for¹³⁷Cs, and 19±8 pCi/kg and 12±4 pCi/kg for^239,240Pu The behavior of^239,240Pu and¹³⁷Cs within the water column is shown to diverge within brackish waters Specifically, the magnitude of the¹³⁷Cs distribution coefficient (K _d ) can be expressed as an inverse power function of the chloride ion concentrations for chlorinities between 0.1 and 4 g Cl⁻/l No difference in the^239,240PuK _d has been observed between fresh and brackish waters Based on the expected inventories of^239,240Pu and¹³⁷Cs within watershed soils, the current downstream transport of these radionuclides represents fractional mobilization rates on the order of 1–4 (×10⁻⁴) per year     

Plutonium, 241Am and 137Cs ratios,inventories and vertical profiles in Washington and Oregon continental shelf sediments

Continental shelf sediments from nine locations off Washington and Oregon have ^239,240Pu inventories which average 8.0 ± 2.6 mCi/km². The Columbia River and seawaters advecting over the shelf supply Pu which is removed to underlying sediments, principally through scavenging by inorganic paniculate matter. Mass balance calculations argue that less than 20 percent of the advected Pu need be scavenged from the water column to balance river input and total shelf sediment inventories. The percentage of the Pu removed through scavenging is consistent with observed participate concentrations in shelf waters and published sediment/water distribution coefficients.No marked separation of Pu from ¹³⁷Cs is observed with depth in Pacific shelf sediments as has been reported in Atlantic coastal sediments. This interocean distinctness can be explained by differences in particle mixing and downward diffusion of Cs in sediments of varying porosities. The transuranic inventories and Pu/Cs ratios in the Pacific sediments do not support the hypothesis of Livingston and Bowen that Pu is remobilized within the sediment column by ‘complexone’ formation with (principally) organic substances.Excess ²¹⁰Pb/^239,240Pu inventory ratios in eight representative cores from the Washington shelf average 100 ± 19, even though absolute values of both inventories vary by much larger factors. This reasonably constant ratio, for a given water depth, permits estimation of total Pu inventories and prediction of sites of unusual Pu accumulation from data on the more easily measured natural radionuclide.     

Solubility and sorption of redox-sensitive radionuclides (Np,Pu) in J-13 water from the Yucca Mountain site: comparison between experiment and theory

This study presents the characterization of Pu-bearing precipitates and the results from uptake studies of Np and Pu on inorganic colloidal particulates in J-13 water from the Yucca Mountain site. Plutonium solubilities determined experimentally at pH values of 6, 7, and 8.5 are about two orders of magnitude higher than those calculated using the existing thermodynamic database indicating the influence of colloidal Pu(IV) species. Solid phase characterization using X-ray diffraction revealed primarily Pu(IV) in all precipitates formed at pH 6, 7, and 8.5. The solubility controlling Pu-bearing solids precipitated at ambient temperature consisted of amorphous Pu(OH)₄(s) with several Pu–O distances between 2.3 and 2.7 Å that are characteristic for Pu(IV) colloids. High temperature (90 °C) increased solid phase crystallinity and produced Pu(IV) solids that contained Pu oxidation state impurities. X-ray absorption spectroscopic studies revealed diminished Pu–O and Pu–Pu distances that were slightly different from those in crystalline PuO₂(s). A Pu–O bond of 1.86 Å was identified that is consistent with the plutonyl(V) distance of 1.81 Å in PuO₂⁺(aq). Hematite, montmorillonite, and silica colloids were used for uptake experiments with ²³⁹Pu(V) and ²³⁷Np(V). The capacity of hematite to sorb Pu significantly exceeded that of montmorillonite and silica. A low desorption rate was indicative of highly stable Pu-hematite colloids, which may facilitate Pu transport to the accessible environment. Neptunium uptake on all mineral phases was far less than Pu(V) uptake suggesting that a potential Pu(V)–Pu(IV) reductive sorption process was involved. The temperature effect on Pu solubility and pseudocolloid formation is also discussed.     

The adsorption of plutonium IV and V on goethite

The adsorption of Pu(IV) and Pu(V) on goethite (αFeOOH) from NaNO₃ solution shows distinct differences related to the different hydrolytic character of these two oxidation states. Under similar solution conditions, the adsorption edge of the more strongly hydrolyzable Pu(IV) occurs in the pH range 3 to 5 while that for Pu(V) is at pH 5 to 7. The adsorption edge for Pu(V) shifts with time to lower pH values and this appears to be due to the reduction of Pu(V) to Pu(IV) in the presence of the goethite surface. These results suggest that redox transformations may be an important aspect of Pu adsorption chemistry and the resulting scavenging of Pu from natural waters.Increasing ionic strength (from 0.1 M to 3 M NaCl or NaNO₃ and 0.03 M to 0.3 M Na₂SO₄) did not influence Pu(IV) or Pu(V) adsorption. In the presence of dissolved organic carbon (DOC), Pu(V) reduction to Pu(IV) occurred in solution. Pu(IV) adsorption on goethite decreased by 30% in the presence of 240 ppm natural DOC found in Soap Lake, Washington waters. Increasing concentrations of carbonate ligands decreased Pu(IV) and Pu(V) adsorption on goethite, with an alkalinity of 1000 meq/l totally inhibiting adsorption.The Pu-goethite adsorption system provides the data base for developing a thermodynamic model of Pu interaction with an oxide surface and with dissolved ligands, using the MINEQL computer program. From the model calculations we determined equilibrium constants for the adsorption of Pu(IV) hydrolysis species. The model was then applied to Pu adsorption in carbonate media to see how the presence of CO₃^?2 could influence the mobility of Pu. The decrease in adsorption appears to be due to formation of a Pu-CO₃ complex. Model calculations were used to predict what the adsorption curves would look like if Pu-CO₃ complexes formed.     

Migration of transuranic elements in groundwater from the near-surface radioactive waste site

Field experiments and laboratory studies were performed to investigate migration processes of plutonium isotopes from a near-surface radioactive waste trench to the underlying sandy aquifer at the Red Forest waste dump in the Chernobyl zone. The objectives of these experiments were to characterize the spatial distribution and possible migration mechanisms of plutonium in the aquifer. During 2002–2007 experimental investigations were carried out and spatial distributions of plutonium isotopes (^239,240Pu, ²³⁸Pu), ⁹⁰Sr and major ions in the aquifer in the direction of the groundwater flow were obtained. Specific activities of radionuclides in groundwater depended on the location of the piezometer and varied in the range of 1–360 mBq kg⁻¹ for ^239,240Pu, 0.5–180 mBq kg⁻¹ for ²³⁸Pu and n–n·10⁴ Bq kg⁻¹ for ⁹⁰Sr. It was found that the spatial features of the distributions of plutonium and strontium specific activities in the upper eolian aquifer were similar, i.e. there was a correlation between the positions of the activity maxima of the radionuclides. The Pu isotopes plume in the aquifer spreads about 15 m downstream of the radionuclides source. Characterization of the initial radionuclide composition of the waste showed that all plutonium in the aquifer originated from the trench. The ratio of plutonium isotopes (^239,240Pu/²³⁸Pu) at the sampling time was the same in waste material and in groundwater samples. In situ ultrafiltration of several groundwater samples was carried out. The size fractionation data obtained suggest that a significant part of plutonium (50–98%) in the groundwater sampled close to the source from the upper part of the aquifer is associated with a very low molecular weight fraction (<1 kDa).     

Downward migration of Chernobyl-derived radionuclides in soils in Poland and Sweden

Vertical profiles of ¹³⁷Cs and ^239,240Pu were measured in soils collected from two sites in southern Sweden and three sites in southern Poland and were modeled using both a solute transport model and a bioturbation model to better understand their downward migration. A time series of measured ¹³⁷Cs profiles indicates that ¹³⁷Cs from Chernobyl was found at the soil surface in 1986 but it has migrated progressively downward into the soil 4.5-25.5 cm since. However, because of dispersion during the migration and mixing following Chernobyl deposition and the much higher activities of ¹³⁷Cs from Chernobyl, stratospheric fallout of ¹³⁷Cs from the 1960s cannot be identified as a second ¹³⁷Cs activity maximum lower in the soil column at any of the sites. Conversely, the ²⁴⁰Pu/²³⁹Pu ratio indicates that no Chernobyl-derived Pu is present in any of the cores with the exception of one sample in Sweden. This difference may be attributed to the nature of the release from Chernobyl. Cesium volatilized at the reactor temperature during the accident, and was released as a vapor whereas Pu was not volatile and was only released in the form of minute fuel particles that traveled regionally. Both the solute diffusion and the bioturbation models accurately simulate the downward migration of the radionuclides at some sites but poorly describe the distributions at other sites. The distribution coefficients required by the solute transport model are about 100 times lower than reported values from the literature indicating that even though the solute transport model can simulate the profile shapes, transport as a solute is not the primary mechanism governing the downward migration of either Cs or Pu. The bioturbation model uses reported values from the literature of the distribution coefficients and can simulate the downward migration because that model buries the fallout by placing soil from depth on top and mixing it slightly throughout the mixing zone (0.6-2% per year of mixing). However, mixing in that model predicts concentrations in the top parts of the soil profiles which are too high in many cases. Future progress at understanding the downward migration of radionuclides and other tracers will require a more comprehensive approach, combining solute transport with bioturbation and including other important soil processes.     

The behaviour of dissolved organic material,iron and manganese in estuarine mixing

Fractionation by ultra-filtration of the dissolved organic material (DOM) in the River Beaulieu, with typical concentrations of dissolved organic carbon (DOC) of 7–8 mg C/l, showed it to be mainly in the nominal molecular weight range of 10³–10⁵, with 16–23% of the total DOC in the fraction > 10⁵. The molecular weight distribution of DOM in the more alkaline River Test (average DOC, 2 mg C/l) was similar. In the River Beaulieu water, containing 136–314 βg Fe/l in ‘dissolved’ forms, 90% or more of this Fe was in the nominal molecular weight fraction > 10⁵. Experiments showed that DOM of nominal molecular weight <10⁵ could stabilize Fe(III) in ‘dissolved’ forms. The concentrations of ‘dissolved’ Fe in the river water probably reflect the presence of colloidal Fe stabilized by organic material and this process may influence the apparent molecular weight of the DOM. Dissolved. Mn (100–136 βg/l) in the River Beaulieu was mainly in true solution, probably as Mn(II), with some 30% in forms of molecular weight greater than ca 10⁴.During mi xing in the Beaulieu Estuary, DOC and dissolved Mn behave essentially conservatively. This contrasts with the removal of a large fraction of the dissolved Fe (Holliday and LISS, 1976, Est. Coastal Mar. Sci. 4, 349–353). Concentrations of lattice-held Fe and Mn in suspended particulate material were essentially uniform in the estuary, at 3.2 and 0.012%, respectively, whereas the non-lattice held fractions decreased markedly with increase in salinity. For Mn the decrease was linear and could be most simply accounted for by the physical mixing of riverborne and marine participates, although the possibility that some desorption occurs is not excluded. The non-linear decrease in the concentration of non-lattice held Fe in particulates reflected the more complex situation in which physical mixing is accompanied by removal of material from the ‘dissolved’ fraction.     

Sources and vertical distribution of 137Cs, 238Pu, 239+240Pu and 241Am in peat profiles from southwest Spitsbergen

This paper presents a detailed survey of the activities of selected man-made radionuclides in peat deposits located in SW Spitsbergen. Peat cores from the High Arctic (SW Spitsbergen) were analyzed by gamma spectrometry (¹³⁷Cs), alpha spectrometry (²³⁸Pu, ^239,240Pu, ²⁴¹Am activities) and by ICPMS (²⁴⁰Pu/²³⁹Pu atom ratios). Maximum activities evident in the peats correspond to the 1963/1964 global maximum fallout from atmospheric testing of nuclear weapons; some of the activity profiles have been altered post-deposition by water infiltration. Activity ratios of ²³⁸Pu/^239+240Pu, ²⁴¹Am/^239+240Pu, ^239+240Pu/¹³⁷Cs and ²⁴⁰Pu/²³⁹Pu atom ratios indicate mixing between global (stratospheric) and regional (tropospheric) sources of these radionuclides in the Svalbard area. The ²³⁸Pu/^239+240Pu activity ratios varied from 0.02 ± 0.01 to 0.09 ± 0.03, suggesting global fallout as the dominant source of Pu. The ^239+240Pu/¹³⁷Cs activity ratios varied from 0.01 ± 0.01 to 0.42 ± 0.11, which apparently arises from the post-depositional mobility of ¹³⁷Cs. The ²⁴¹Am/^239+240Pu activity ratios ranged between 0.10 ± 0.02 and 1.5 ± 0.3 and exceed the published global fallout ratio for Svalbard of 0.37 due to the relatively higher geochemical mobility of Pu vs. Am and/or ingrowth of Am from the decay of ²⁴¹Pu. The atom ratio ²⁴⁰Pu/²³⁹Pu ranged from 0.142 ± 0.006 to 0.241 ± 0.027; however, the vast majority of peat samples exhibited ²⁴⁰Pu/²³⁹Pu atom ratios similar to the stratospheric fallout (∼0.18).     

Sorption-desorption behavior of strontium-85 onto montmorillonite and silica colloids

Strontium-90 (⁹⁰Sr) is one of the major radioactive contaminants found in DP Canyon at Los Alamos, New Mexico, USA. Radioactive surveys found that ⁹⁰Sr is present in surface water and shallow alluvial groundwater environments in Los Alamos National laboratory (LANL). Colloids may influence the transport of this radionuclide in surface and groundwater environments in LANL. In this study, the authors investigated the sorption/desorption behavior of radioactive Sr on Ca-montmorillonite and silica colloids, and the effect of ionic strength of water on the sorption of Sr. Laboratory batch sorption experiments were conducted using ⁸⁵Sr as a surrogate for ⁹⁰Sr. Groundwater, collected from Well LAUZ-1 at DP Canyon and from Well J-13 at Yucca Mountain, Nevada, and deionized water, were used. The results show that 92–100% of the ⁸⁵Sr was rapidly adsorbed onto Ca-montmorillonite colloids in all three waters. Adsorption of ⁸⁵Sr onto silica colloids varied among the three waters. The ionic strength and Ca²⁺ concentration in groundwater significantly influence the adsorption of ⁸⁵Sr onto silica colloids. Desorption of ⁸⁵Sr from Ca-montmorillonite colloids is slower than from silica colloids. Desorption of ⁸⁵Sr from silica colloids was faster in LAUZ-1 groundwater than in J-13 groundwater and deionized water. The results suggest that clay and silica colloids may facilitate the transport of Sr along potential flowpaths from DP Canyon to Los Alamos Canyon.